Method of deodorizing the human body and materials therefor



Unit

The present application relates in general to material with deodorizing action, in particular to hygienic articles and preparations, such as sanitary napkins, vaginal tampons, diapers, dress-preservers, insoles or supports for use in shoes, body-powders, hygienic creams, soaps, body-hygiene liquids and the like, which contain a deodorant or are impregnated therewith or contain parts impregnated with the deodorant. It further relates to a method of deodorizing the human body by applying thereto such deodorant material.

The present patent application is a continuation in part application of our pending patent application Ser. No. 761,701, filed on September 18, 1958, now abandoned.

Materials known as disinfectants have already been used in the production of deodorizing preparations and hygienic products. For this purpose there have been used in the prior art for instance 2,2-dihydroXy-3,5,6,3,5',6'- hexachloro-diphenylmethane, quaternary ammonium compounds, organic mercury compounds, phenol derivatives with and without halogen substituents or amino acid derivatives that are efiective against bacteria. However, these substances are disadvantageous in that their eilectiveness is largely annulled in the presence of protein, e.g. blood. Their efiectiveness is due to a disadvantageous destruction of the bacterial skin flora which causes the decomposition of the sweat and thus the efiluviurn.

It has also been proposed to use chlorophyll as the de odorant. However, the effectiveness of this agent is questioned and is even denied, as may be seen from J. Amer. Med. Assoc. 147, 99, 1951, as well as from other references. Actually, it is no longer used today when a deodorizing effect is desired. Tests of our own relating to the use of chlorophyll in the menstrual hygiene have shown that when using cellulose fibers containing 0.4 per cent of chlorophyll or more, strong decomposition odors cannot be avoided, whereas when using the new deodorants described hereinafter there are no decomposition odors at all even at far lower concentrations of the deodorant.

It is furthermore known to use for the purpose of de odorization agents that act purely adsorptively, such as gels of aluminum or silicon oxide hydrates, or salts of polyvalent metals such as aluminum, zinc, tin, zirconium both in inorganic and organic linkage, or complex compounds of said metals, such as trisodium-dialuminum pentahydroXychloro-lactate and sodium-zirconium-lactate. It was found, however, that the decdorizing action of the zirconium compounds results only from their penetration into the fine perspiratory capillaries, whereby the colloid protein precipitates in the perspiratory canals and coagulates to form an insoluble hydrophobe substance. Thus, there is involved a protein precipitation which prevents secretion and damages the epithelium, whereby the further throw-out of sweat is inhibited by blockage of the apocrinic glands. Thus, an excessive secretion of sweat is indeed prevented, but, simultaneously, the danger of skin damages is brought about.

The use of bactericide antibiotics as deodorants is out of the question for several reasons, all of which are not referred to at this point. We refer here only to the danger of cultivating therapy-resistant germs, to the inefiectiveness of most of the antibiotics with respect to the gram-negative microorganisms that especially produce a particularly strong odor, to their instability and to the price of the antibiotics.

Now we have found that a group of compounds never before suggested for such purpose is most suitable as deodorants and are superior to all deodorants known in the art. These new deodorants are water-soluble betadiketone metal salts of polyvalent metals. In general, all polyvalent metals, insofar as they form at least slightly water-soluble salts with the beta-diketones, can be used. However, for practical reasons, some metals are less suited, is. those whose beta-diketone salts are too toxic or too expensive or too much colored or tend to decompose. Beta-diketone metal salts well suited for the present purpose are those of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt. Particularly preferred are the copper, aluminum, magnesium, cobalt and zirconium salts.

The metal salts must be water-soluble, at least to a low extent.

The beta-diketones suitable for being used in the salt formation are those containing the atom grouping t Y-O O-CHCOY wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloxy, alkyl, aryl and aralkyl and Y represents substituted or unsubstituted alkyl, aralkyl or aryl radicals. The following diketones are preferred:

2,4-pentanedione 3chloro-2,4-pentanedione 4-pmethylphenyl-2,4-butanedione 4-p-aminophenyl-2,4-butanedione 3-n-dodecyl-2,4-pentanedione 4-phenyl-2,4-butanedione The action of the new metal salt deodorants is superior to that of the known agents. They remain active in the presence of blood. The perspiratory capillaries are not blocked, the skin flora is not destroyed and the skin is not damaged. In addition thereto, said metal salts do not show the disadvantages encountered when using antibiotics.

The effectiveness of the new deodorants probably is caused by the fact that they merely intervene in the metabolism of the bacteria and other microorganisms, such as fungi, thus preventing the formation of undesired excretory products. Even if the growth of bacteria or microorganisms is not or is not completely suppressed when a subliminal dosage is used, the formation and excretion of undesired odor-forming substances is nevertheless prevented. Hence, a low dosage is often suihcient. Thus, if the dosage is appropriately chosen, the symbiotic flora is completely preserved, which is very desirable for reasons of health, as in the preservation of the mucosa flora.

The new deodorants may be used in different forms.

For instance, fibers or fibrous materials, particularly those made of cellulose, may be impregnated with these agents. Alternatively, the new agents may be used as components in the preparation of powders, soaps, liquids or the like. The present deodorants may be applied onto or incorporated into the base materials used, such as fibers or fibrous materials, ointrnents, powders, soaps, liquids or the like, in any manner known per se, e.g. by floating, impregnating, spraying, wetting or printing by means of a solution of the agent in water or in an organic solvent.

The following examples serve to illustrate the present invention.

Example 1 720 g. of copper acetylacetone, prepared in known manner from acetylacetone (2,4-pentanedione) and copper acetate, are dissolved in 32 liters of hot ethyl alcohol and poured into a fine aqueous suspension contining 360 kg. of highly adsorptive cellulose which had been prepared by grinding in a hollander with 6 m. of water until it showed the desired degree of fineness. Then the suspension runs over the paper machine and the thus pre pared cellulose wadding is used for the manufacture of sanitary napkins. Even after having been stored for a long period of time, these napkins have a substantially complete deordorizing action.

Example 2 Cellulose Wadding fleeces, during their being doubled, are sprayed outside of the paper machine with an 8% aqueous suspension of copper -phenyl-2,4-pentanedione, prepared from copper acetate and 5-phenyl-2,4-pentanedione, in order to obtain a great surface activity, said spraying being carried out by means of compression jets or air nozzles, diffusers or aerosol atomizer in such a manner that a very finely divided deposit of -30 mg. per 10 g. of cellulose wadding results after drying. Thus treated cellulose wadding shows a surprising dcodorizing action when being used as the adsorbing part of sanitary napkins.

Example 3 10 parts of 2,4-heptanedione zirconate, obtainable by reacting 2,4-heptanedione with zirconium acetate, are worked into 1000 parts of a usual powder base. This powder exhibits good deodorant properties.

Example 4 A fat melt is prepared in the following manner: 200 parts by weight of adeps lanae, parts by weight of beeswax and 100 parts by weight of oleurn olivarum are melted together in the common manner in a water bath and are heated to about 75 C.

In another vessel, 100 parts by weight of aqua destillata, 100 parts by weight of ethyl alcohol and 2.5 par-ts by weight of the calcium complex compound of heptanedione, prepared from 2,4-heptanedione and calcium carbonate in boiling Water, are heated likewise to 75 C. and the mixture obtained is added to the above fat melt in the form of a thin stream While stirring until the whole batch has cooled down. The finished cream may be perfumed as desired by adding perfume oils. The cream is allowed to stand for one day and on the other day it is filled into boxes or tubes. This cream suppresses unpleasant body odor.

Example 5 An alcoholic solution of 500 g. of the cadmium complex compound of hexanedione, obtainable by reacting 2,4-hexanedione with cadmium acetate in known manner, is Worked into an aqueous suspension of 100 kg. of cellulose. The sanitary napkins manufactured from said cellulose wadding exhibit substantially complete deodorant action even after having been worn for a long time.

Example 6 100 kg. of crude textile wadding are impregnated in a mixing apparatus with 200 g. of the magnesium complex compound of acetylacetone, obtained in the usual manner by reacting magnesium carbonate with acetylacetone, the complex compound being dissolved in 10 liters of 70% isopropyl alcohol. After evaporation of the alcohol the thus obtained, impregnated wadding is used for manufacturing vaginal tampons, the deodorant properties of which are superior to those of the normal tampons.

Example 7 Diapers are prepared from cellulose fibers or textile fibers, to which are added during or after their being finished 2 percent of the aluminum complex compound of acetylacetone, obtainable by reacting aluminum chloride with acetylacetone in the usual manner, said addition being made by spraying, printing, coating, foaming or dipping.

Example 8 A finished fiber fleece is printed with a paste which was prepared by mixing 1000 g. of water, g. of the copper complex compound of 3-chloro-2,4-pentanedione, obtained by reacting 3-chloro-2,4-pentanedione with copper acetate, and 0.5 percent of carboxymethyl cellulose. From the thus obtained fiber fleece insoles or supports for use in shoes are manufactured.

Example 9 A finished fiber fleece is printed with a paste which was prepared by mixing 1000 g. of Water, 100 g. of the copper complex compound of the p-aminobenzoyl acetone, obtained from p-aminobenzoyl acetone and copper acetate, and 0.5 percent of carboxymethyl cellulose. From the thus obtained fiber fleece insoles or supports for use in shoes are manufactured.

Example 10 Fiber fleece having a weight of 20 g. per m2 is passed in a suitable apparatus through a solution of the copper complex compound of the 3-acetoxy-2,4-pentanedione, prepared in known manner from 3-acetoxy-2,4-pentanedione and copper acetate, and is then squeezed out under application of such a pressure that 0.2 g. active substance per 10 g. of fleece will remain after evaporation of the solvent. The fleece thus prepared is most successfully used for manufacturing deodorizing dress shields.

Example 11 Fiber fleece having a weight of 20 g. per 111. is passed in a suitable apparatus through a solution of the copper complex compound of p-methylbenzoyl acetone, obtainable from p-methylbenzoyl acetone and copper acetate, and is then squeezed under application of such a pressure that 0.2 g. of the active agent per 10 g. of the fleece will remain after evaporation of the solvent. The thus obtained fleece is most successfully used for manufacturing deodorizing insoles or supports for shoes.

Example 12 50 kg. of fine-capillary silica gel and 30 kg. of coarsecapillary silica gel are placed in the powder-mixer, and a solution of 500 g. of the calcium complex compound of 2,4-octanedione, prepared for calcium carbonate and 2,4- octanedione in 5 liters of hot ethyl alcohol, is poured into the mixing drum and the Whole is stirred until the alcohol is evaporated. Thereupon, a cream consisting of 7.0 kg. of aqua destillata and 7.5 kg. of adeps lanae is slowly added and the powder is finished by continuing the mixing for five hours.

Example 13 12.0 parts by weight of stearin 1.0 part by weight of isopropyl palmitate 2.0 parts by Weight of sorbitanemonostearate 1.0 part by weight of polyalkyleneoxide sorbitanemonostearate 2.5 parts of sorbite syrup are worked together to form a deodorizing cream Example 14 30 parts by weight of talcum 19 40 parts by weight of silica gel 20 parts by weight of starch 0.5 part by weight of tragacanth 5.0 parts by weight of ethyl alcohol 0.5 part by Weight of the cobalt complex compound of 15 alpha-n-dodecyl-acetylacetone, obtainable by reacting cobalt nitrate with 3-n-dodecyl-2,4-pentanedione and neutralization are mixed and water is added in the amount required for pressing an anti-sweat powder-stick.

Example 15 0.5 part of the calcium complex compound of 2,4-no nanedione, obtainable from calcium carbonate and 2,4- nonanedione, are dissolved in a mixture of 60 parts of ethyl alcohol and 14.0 parts of water by heating. After cooling down 0.5 part of perfume oil is added. Under addition of parts of the propelling agent Frigen (as noted in De Navarres International Encyclopedia of Cosmetic Material Trade Names, 1957, page 116) the product is filled into pressure boxes by use of a suitable apparatus. The thus prepared body spray is most suited for body deodorizing.

Example 16 990 parts of curd soap are melted in the water bath, and a fine slurry consisting of 10 parts of the copper com plex compound of 3-acetyl-2,4-pentanedione, obtainable by reacting 3-acetyl-2,4-pentanedione with copper acetate, in parts of ethyl alcohol is admixed while violently 4 stirring until the batch is uniform. After having poured the latter into soap molds and after having allowed them to stand, the usual procedure is applied.

Example 17 990 parts of curd soap are melted in the water bath, and a fine slurry consisting of 10 parts of the antimony complex compound of acetylacetone, prepared from antimony-penta-chloride in boiling chloroform and acetylacetone, in 50 parts of ethyl alcohol is admixed while 50 violently stirrin until the batch is uniform. After having poured the latter into molds and after having allowed them to stand, the usual procedure is applied.

Example 18 During the manufacture of cellulose wadding, an ethylalcoholic solution of 500 g. of 2-methyl-4,6-heptanedione zirconate, obtained by reacting in known manner 2-methyl- 4,6-heptanedione with zirconium acetate, is worked into the aqueous suspension of 100 kg. of cellulose. The hygienic sanitary napkins manufactured therefrom ex hibit substantially complete deodorant action even after having been worn for a long time.

Example 19 G5 1 part of 2,4-heptanedione zirconate, obtainable by reacting 2,4-heptanedione with zirconium acetate, is dissolved in 1000 parts of 60% ethyl alcohol and the solution is slightly perfumed as may be desired. When the armpit is treated with this solution, no perspiration odor is perceptible.

Example 20 Textile wadding to be used for manufacturing vaginal tampons, prior to its being pressed, is impregnated with 7 0.2 percent based on its dry weight, of the copper complex compound of 2,2-dimethyl-3,S-hexanedione, obtainable by reacting in the usual manner 2,2-dimethyl-3,5-hexanedione with copper acetate.

Example 21 A textile fleece with a weight of 30 g. per square metre is passed through a bath consisting of a 3% suspension of the copper complex salt of 2-methyl-3,S-heptanedione, prepared by reacting copper acetate with 2-methyl-3,5 heptanedione. The fleece is then squeezed under the application of pressure such that 0.2 percent of complex salt, based on the dry weight of the fleece, is retained.

Wrapping diapers manufactured therefrom exhibit no urine decomposition odor even after having been worn for a longer period of time.

We claim:

1. A method of deodorizing the human body which comprises intimately contacting the odoriferous portion of the body surface with an at least slightly water-soluble salt of a beta-diketone having the formula i Y--G0CH-OOY wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloxy, alkyl, aryl and aralkyl and Y is selected from the group consisting of substituted and unsubstituted alkyl, aralkyl and aryl radicals, with a polyan acylacetone.

3. The method of claim 1 wherein the beta-diketone is 2,4-pentanedione.

4. The method of claim 1 wherein the beta-diketone is 3-chloro-2,4-pentanedione.

5. The method of claim 1 wherein the polyvalent metal is copper.

6. The method of claim 1 wherein the polyvalent mteal is aluminum.

7. Sanitary napkins having deodorizing action due to the presence therein of an at least slightly Water-soluble salt of an acylacetone with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt.

8. The sanitary napkins of claim 7 wherein the salt is copper 2,4-pentanedione.

9. Vaginal tampons having deodorizing action due to the presence therein of an at least slightly water-soluble salt of an acylacetone with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and coba t.

10. The vaginal tampons of claim 9 wherein the salt is copper 2,4-pentanedione.

11. A method of deodorizing the human body which comprises intimately contacting the odoriferous portion of the body surface with a sanitary napkin containing an at least slightly water-soluble salt of a beta-diketone having the formula wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloxy, alkyl, aryl and aralkyl and Y is selected from the group consisting of substituted and unsubstituted alkyl, aralkyl and aryl radicals, with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt.

12. A method of deodorizing the human body which comprises intimately contacting the odoriferous portion of the body surface with a cosmetic base having distributed through it an at least slightly water-soluble salt of a betadiketone having the formula wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloXy, alkyl, aryl and aralkyl and Y is selected from the group consisting of substituted and unsubstituted alkyl, aralkyl and aryl radicals, with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt.

13. A method according to claim 12 wherein the cosmetic base is a soap.

14. A method according to claim 12 wherein the cosmetic base is an ointment.

15. A method of deodorizing the human body which comprises intimately contacting the odoriferous portion of the body surface with a vaginal tampon containing an at least slightly Water-soluble salt of a beta-diketone having the formula wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloxy, alkyl, aryl and aralkyl and Yis selected from the group consisting of substituted and unsubstituted alkyl, aralkyl and aryl radicals with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt.

16. A method of deodorizing the human body which comprises intimately contacting the odoriferous portion of the body surface with a diaper containing an at least slight- 1y water-soluble salt of a beta-diketone having the formu- 1a wherein X is selected from the group consisting of hydrogen, halogen, acyl, acyloxy, alkyl, aryl and aralkyl and Y is selected from the group consisting of substituted and unsubstituted alkyl, aralkyl and aryl radicals with a polyvalent metal selected from the group consisting of copper, magnesium, calcium, zinc, cadmium, aluminum, zirconium, antimony and cobalt.

References Cited in the tile of this patent UNITED STATES PATENTS 1,736,448 Liebknecht Nov. 19, 1929 2,149,856 McKOnc Mar. 7, 1939 2,208,253 Flenner July 16, 1940 2,313,621 Bruson Mar. 9, 1943 2,564,855 Neff Aug. 21, 1951 2,976,285 Gash Mar. 21, 1961 FOREIGN PATENTS 786,411 Great Britain Nov. 20, 1957 OTHER REFERENCES 

11. A METHOD OF DEODORIZING THE HUMAN BODY WHICH COMPRISES INTIMATELY CONTACTING THE ODORIFEROUS PORTION OF THE BODY SURFACE WITH A SANITARY NAPKIN CONTAINING AN AT LEAST SLIGHTLY WATER-SOLUBLE SALT OF A BETA-DIKETONE HAVING THE FORMULA 